EP2850121B1 - Hochleistungs-polysulfone aus cycloaliphatischen diolen - Google Patents

Hochleistungs-polysulfone aus cycloaliphatischen diolen Download PDF

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Publication number
EP2850121B1
EP2850121B1 EP13723756.6A EP13723756A EP2850121B1 EP 2850121 B1 EP2850121 B1 EP 2850121B1 EP 13723756 A EP13723756 A EP 13723756A EP 2850121 B1 EP2850121 B1 EP 2850121B1
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Prior art keywords
polymer
poly
arylethersulfone
group
membranes
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French (fr)
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EP2850121A1 (de
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Atul Bhatnagar
Hong Chen
Chantal Louis
Narmandakh TAYLOR
Joel POLLINO
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Solvay Specialty Polymers USA LLC
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Solvay Specialty Polymers USA LLC
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/20—Polysulfones
    • C08G75/23—Polyethersulfones
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/08—Hollow fibre membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
    • B01D71/68—Polysulfones; Polyethersulfones
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D1/00—Containers having bodies formed in one piece, e.g. by casting metallic material, by moulding plastics, by blowing vitreous material, by throwing ceramic material, by moulding pulped fibrous material, by deep-drawing operations performed on sheet material
    • B65D1/02—Bottles or similar containers with necks or like restricted apertures, designed for pouring contents
    • B65D1/0207—Bottles or similar containers with necks or like restricted apertures, designed for pouring contents characterised by material, e.g. composition, physical features
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]

Definitions

  • the invention relates to new poly(arylethersulfone) polymers comprising cycloaliphatic moieties featuring exceptional properties.
  • the invention further relates to methods of manufacturing the invented polymers, compositions containing such polymers, and articles made from such polymers.
  • Poly(arylethersulfone) is a generic term used to describe any polymer containing at least one ether group (-O-), at least one sulfone group (-SO 2 -) and at least one arylene group.
  • a commercially important group of poly(arylethersulfones) includes polysulfone polymers identified herein as PSU.
  • PSU contains reacted units of diphenyl sulfone and bisphenol A (BPA).
  • BPA bisphenol A
  • Such PSU is commercially available from Solvay Specialty Polymers, L.L.C. (i.e., under the trademark UDEL®).
  • the structure of the repeating units of a UDEL polysulfone is made by condensing bisphenol A (BPA) and 4,4'-dichlorodiphenyl sulfone (DCDPS).
  • PSU has a glass transition temperature of about 185°C and exhibits high strength and toughness.
  • RADEL® polyphenylsulfone, identified herein as PPSU
  • PPSU polyphenylsulfone
  • L.L.C. Solvay Specialty Polymers, L.L.C. which is made by reacting units of 4,4'-dichlorodiphenyl sulfone (DCDPS) and 4,4'-biphenol (BP).
  • DCDPS 4,4'-dichlorodiphenyl sulfone
  • BP 4,4'-biphenol
  • polysulfones include co-polymers having at least two different types of sulfone and/or diphenol groups.
  • VERADEL® polyethersulfones available from Solvay Specialty Polymers, L.L.C., include a polyethersulfone portion made from repeating or recurring groups of formula -Ar-SO 2 -Ar-O-, wherein Ar is a substituted or unsubstituted aryl group such as a phenyl, biphenyl, bisphenol or any other aryl group containing an aromatic or hetero-aromatic ring.
  • poly(aryl ether sulfones) Because of their excellent mechanical and thermal properties, coupled with outstanding hydrolytic stability and chemical resistance, poly(aryl ether sulfones) have been used for making products in various and diverse applications handling a broad range of end-use temperatures (from - 40°C to 204°C), such as plumbing articles, food service articles, medical trays, membranes etc.
  • poly(arylethersulfones) from which the repeating units are derived from bisphenol A (BPA) such as notably in UDEL® polysulfones or/and derived from 4,4'-biphenol (BP) such as notably in RADEL® polyphenylsulfones is that said poly(arylethersulfone) polymers can be adversely affected by long term exposure to UV light.
  • BPA bisphenol A
  • BP 4,4'-biphenol
  • It is another object of the present invention a poly(arylethersulfone) polymer consisting essentially of recurring units derived from the direct reaction from at least one aromatic dihalocompound comprising at least one -S( O) 2 -group and at least one diol (D) having general formula (I) HO-Q-OH (I) wherein Q is a group comprising from 4 to 30 carbon atoms, preferably from 8 to 15 which comprises at least one cycloaliphatic moiety (M), with the proviso that said cycloaliphatic moiety (M) does not comprise any heteroatoms in the ring, and said poly(arylethersulfone) polymer is having a number average molecular weight (M n ) of above 8 000.
  • the poly(arylethersulfone) polymer has advantageously a number average molecular weight (M n ) above 10 000, more preferably above 12 000, more preferably above 15 000 and more preferably above 20 000.
  • the poly(arylethersulfone) polymer has advantageously a number average molecular weight (M n ) equal to or below 120 000, preferably equal to or below 100 000, preferably equal to or below 90 000, preferably equal to or below 80 000, preferably equal to or below 70 000 preferably equal to or below 68 000, preferably equal to or below 55 000.
  • M n number average molecular weight
  • the poly(arylethersulfone) polymer has advantageously a number average molecular weight (M n ) in the range from 8 000 to 100 000 preferably ranging from 10 000 to 80 000, preferably ranging from 12 000 to 70 000.
  • M n can be suitably determined by gel-permeation chromatography (GPC), calibrated with polystyrene standards.
  • the polydispersity index (PDI) is hereby expressed as the ratio of weight average molecular weight (M w ) to number average molecular weight (M n ).
  • the poly(arylethersulfone) polymer of the present invention has advantageously a polydispersity index (PDI) of more than 1.5, preferably more than 1.90, more preferably more than 2.00.
  • PDI polydispersity index
  • the poly(arylethersulfone) polymer of the present invention has advantageously a polydispersity index (PDI) of less than 4.0, preferably of less than 3.8, preferably of less than 3.5.
  • PDI polydispersity index
  • the fraction of polymer molecules comprised in the poly(arylethersulfone) polymer having a molecular weight of below 3000 [% fraction M ⁇ 3000 , hereinafter] with respect to all the polymer molecules in said poly(arylethersulfone) polymer is advantageously below 10 %, preferably below 8 % and more preferably below 5 %.
  • aromatic dihalocompounds suitable to the purpose of the present invention are compounds of general formula (II) : X-[Ar 3 -SO 2 -Ar 4 ]-[Ar 5 ] n -[Ar 3 -SO 2 -Ar 4 ] m -X (II) wherein n and m are independently 0, 1, 2, 3 or 4 ; wherein X is an halogen selected from chlorine, fluorine, bromine and iodine ; wherein Ar 3 , Ar 4 are equal or different from each other and are aromatic moieties of the formula : wherein Ar 5 is selected from the group consisting of : wherein Ri are independently selected from the group consisting of : hydrogen, halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali or alkaline earth metal sulfonate, alkyl sulfonate, alkal
  • n and m are preferably independently 0, 1 or 2, more preferably n and m are 0 or 1.
  • X is preferably selected from F and Cl.
  • each Ri is preferably independently selected from the group consisting of hydrogens and halogens, more preferably all Ri's are hydrogens.
  • the above mentioned compounds of general formula (II) may notably be one of the following molecules : where X may be the same or different and are any halogen atoms chosen from chlorine, fluorine, bromine and iodine.
  • X may be the same or different and are any halogen atoms chosen from chlorine, fluorine, bromine and iodine.
  • the above structure may also be substituted by groups similar to the Ri described above.
  • the compounds of general formula (II) may be a dihalodiphenyl sulfone such as 4,4'-dichlorodiphenyl sulfone, 4,4'-difluorodiphenyl sulfone, 4,4'-dibromodiphenyl sulfone and 4,4'-diiododiphenyl sulfone or mixed derivatives.
  • the most preferred aromatic dihalocompounds is 4,4'-dichlorodiphenyl sulfone.
  • the most preferred aromatic dihalocompounds is 4,4'-difluorodiphenyl sulfone.
  • the compounds of general formula (II) may also be 4,4'-bis-(4-chlorophenylsulfonyl)biphenyl or 4,4"-bis-(4-chlorophenylsulfonyl)terphenyl.
  • the diol (D) comprises preferably at least one cycloaliphatic moiety (M).
  • cycloaliphatic moiety is intended to denote any moiety being both aliphatic (i.e, not aromatic) and cyclic (i.e., where the carbon atoms are connected in a ring).
  • the cycloaliphatic moiety (M) may comprise from 4 to 8 carbon atoms, preferably from 4 to 6 carbon atoms. It may be either unsubstituted or substituted.
  • the cycloaliphatic moiety (M) does not comprise any heteroatoms in the ring.
  • the backbone of the cycle of the cycloaliphatic moiety is made only of interconnected carbon atoms.
  • More than one cycloaliphatic moiety (M) can be present in diol (D). If more than one cycloaliphatic moiety (M) is present in diol (D), they can be the same or different.
  • the diol (D) has a general formula (D I ): wherein
  • Diol (D) may also comprise a polycyclic cycloaliphatic moiety, said polycyclic cycloaliphatic moiety comprising more than one condensed cycloaliphatic moieties (M).
  • the polycyclic cycloaliphatic moiety comprises two condensed cycloaliphatic moieties (M), three condensed cycloaliphatic moieties (M) or even four condensed cycloaliphatic moieties (M).
  • Each condensed cycloaliphatic moiety (M) typically comprises from 4 to 8 carbon atoms, preferably from 4 to 6 carbon atoms.
  • diol according to general formula (D I ) may exist in different stereochemical and regiochemical arrangements.
  • the two hydroxyl groups may have a cis or trans configuration towards each other.
  • Suitable diol (D) can be selected from the group consisting of: and
  • the diol (D) is of formula (D-5), as shown below :
  • Diols according to formulae (D-1) to (D-5) may exist in different stereochemical arrangements.
  • the stereochemistry of the bonds in particular the stereochemical arrangement of the C-OH or C-CH 2 OH bonds in formulae (D-1) to (D-5), is not indicated in the present specification. It has to be understood that all stereoisomers, each one singly as well as their mixtures, are encompassed by each formula (D-1) to (D-5).
  • formula (D-1) encompasses the cis isomer, the trans isomer, as well as their mixtures in any proportion.
  • the poly(arylethersulfone) polymer according to the present invention comprises the following recurring unit: ⁇ -[Ar 3 -SO 2 -Ar 4 ]-[Ar 5 ] n -[Ar 3 -SO 2 -Ar 4 ] m -O-Q-O- ⁇ (III).
  • the poly(arylethersulfone) polymer according to the present invention comprises advantageously more than 10 % wt, preferably more than 30 % wt, more preferably more than 50 % wt, still more preferably more than 70 % wt and most preferably more than 90 % wt of recurring units of formula (III).
  • excellent results were obtained when the poly(arylethersulfone) polymer according to the present invention consisted of recurring units of formula (IV) and (V) :
  • the poly(arylethersulfone) polymer within the different embodiments can further comprise recurring units derived from an aromatic diol (AD), which is different from the diol (D).
  • AD aromatic diol
  • Any aromatic diol which is able to polymerize with the aromatic dihalocompound (II) is suitable to be used as aromatic diol (AD).
  • Non limitative examples of such aromatic diols (AD) are 4,4'-biphenol (i.e.
  • 4,4'-dihydroxybiphenyl bisphenol A, 4,4'-dihydroxy-diphenylsulfone (also known as bisphenol S), hydroquinone, 4,4'-dihydroxy-diphenylether, alpha, alpha'-bis-(4-hydroxyphenyl)-p-diisopropylbenzene, 1,4-bis(4-hydroxyphenoxy)benzene.
  • a poly(arylethersulfone) polymer comprising recurring units derived from a 4,4'-dihalodiphenylsulfone and a diol selected from the group consisting of those complying with formulae (D-1) and/or (D-2) as detailed above, is especially preferred.
  • the poly(arylethersulfone) polymers of the present invention presents a glass transition temperature of advantageously more than 140°C, preferably more than 160°, more preferably more than 180°C, still more preferably more than 200°C, even more preferably more than 225°C and most preferably more than 250°C.
  • the poly(arylethersulfone) polymers of the present invention are advantageously amorphous and transparent.
  • the polycondensation reaction can be carried out according to known methods, i.e., a carbonate method ; an alkali metal hydroxide method ; or a phase transfer catalyzed method.
  • the poly(arylethersulfone) polymers of the present invention are prepared by a polycondensation reaction which is carried out according to the carbonate method.
  • the process carried out according to the carbonate method is conducted by contacting substantially equimolar amounts of the diol (D) of formula (I) and at least one dihalodiarylsulfone, e.g., 4,4'-dichlorodiphenyl sulfone or 4,4'-difluorodiphenyl sulfone. Excellent results were obtained when using a very large excess of the carbonate.
  • dihalodiarylsulfone e.g., 4,4'-dichlorodiphenyl sulfone or 4,4'-difluorodiphenyl sulfone.
  • the alkali metal carbonate is preferably sodium carbonate, potassium carbonate, rubidium carbonate and cesium carbonate.
  • Sodium carbonate and potassium carbonate are especially preferred.
  • Mixtures of more than one carbonates can be used, for example, a mixture of sodium carbonate or bicarbonate and a second alkali metal carbonate or bicarbonate having a higher atomic number than that of sodium.
  • an alkali metal carbonate having an average particle size of less than about 100 ⁇ m is particularly preferred. More preferably, an alkali metal carbonate average particle size of less than about 50 ⁇ m is used. Still more preferably, an alkali metal carbonate average particle size of less than about 30 ⁇ m is used.
  • the use of an alkali metal carbonate having such a particle size permits the synthesis of the polymers to be carried out at a relatively lower reaction temperature with faster reaction.
  • Sodium and potassium carbonate salts singularly or in combination, may be used to provide polymers having desirable molecular weight characteristics. Higher molecular weight polymers may be obtained when a potassium salt is used.
  • the components are dissolved or dispersed in a solvent mixture comprising a polar aprotic solvent.
  • an additional solvent can be used together with the polar aprotic solvent which forms an azeotrope with water, whereby water formed as a byproduct during the polymerization may be removed by azeotropic distillation continuously throughout the polymerization.
  • the reaction medium is maintained in substantially anhydrous conditions during the polymerization by removing water continuously from the reaction mass. Water can be removed by distillation or with the azeotrope-forming solvent as an azeotrope, as described above.
  • additional solvent is understood to denote a solvent different from the reactants and the products of a given reaction.
  • the polar aprotic solvents employed are those generally known in the art and widely used for the manufacture of poly(arylethersulfones).
  • the sulfur containing solvents known and generically described in the art as dialkyl sulfoxides and dialkylsulfones wherein the alkyl groups may contain from 1 to 8 carbon atoms, including cyclic alkyliden analogs thereof, are disclosed in the art for use in the manufacture of poly(arylethersulfones).
  • sulfur-containing solvents that may be suitable for the purposes of this invention are dimethylsulfoxide, dimethylsulfone, diphenylsulfone, diethylsulfoxide, diethylsulfone, diisopropylsulfone, tetrahydrothiophene-1, 1-dioxide (commonly called tetramethylene sulfone or sulfolane) and tetrahydrothiophene-1-monoxide and mixtures thereof.
  • Nitrogen-containing polar aprotic solvents including dimethylacetamide, dimethylformamide and N-methyl pyrrolidinone (i.e., NMP) and the like have been disclosed in the art for use in these processes, and may also be found useful in the practice of this invention.
  • the additional solvent that forms an azeotrope with water will generally be selected to be inert with respect to the monomer components and polar aprotic solvent.
  • Suitable azeotrope-forming solvents for use in such polymerization processes include aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, chlorobenzene and the like.
  • the azeotrope-forming solvent and polar aprotic solvent are typically employed in a weight ratio of from about 1 : 10 to about 1 : 1, preferably from about 1 : 5 to about 1 : 3.
  • the temperature of the reaction mixture will be maintained in a range of advantageously from 150-220°C for about 3 to 8 hours.
  • the boiling temperature of the solvent selected usually limits the temperature of the reaction.
  • the reaction may be conveniently carried out in an inert atmosphere, e. g., nitrogen, at atmospheric pressure, although higher or lower pressures may also be used.
  • the polymer is treated with an activated aromatic halide or an aliphatic halide such as methyl chloride or benzyl chloride, and the like.
  • an activated aromatic halide or an aliphatic halide such as methyl chloride or benzyl chloride, and the like.
  • Such treatment of the polymer converts the terminal hydroxyl groups into ether groups which stabilize the polymer.
  • the polymer so treated has good melt and oxidative stability.
  • the poly(arylethersulfone) polymers of the present invention are prepared by a polycondensation reaction which is carried out according to the alkali metal hydroxide method.
  • the carbonate method for preparing the polymer of this invention is simple and convenient, in some cases products of higher molecular weight can be made by said alkali metal hydroxide method.
  • a double alkali metal salt of a dihydric phenol is contacted with a dihalobenzenoid compound in the presence of a polar aprotic solvent, e. g.
  • a sulfur containing solvent such as dimethylsulfoxide, dimethylsulfone, diphenylsulfone, diethylsulfoxide, diethylsulfone, diisopropylsulfone, tetrahydrothiophene-1, 1-dioxide (commonly called tetramethylene sulfone or sulfolane) and tetrahydrothiophene-1-monoxide and mixtures thereof under substantially anhydrous conditions.
  • a sulfur containing solvent such as dimethylsulfoxide, dimethylsulfone, diphenylsulfone, diethylsulfoxide, diethylsulfone, diisopropylsulfone, tetrahydrothiophene-1, 1-dioxide (commonly called tetramethylene sulfone or sulfolane) and tetrahydrothiophene-1-monoxide and mixtures thereof under substantially an
  • the poly(arylethersulfone) polymers of the present invention are prepared by a polycondensation reaction which is carried out according to the phase transfer catalyzed method. While the carbonate method and the alkali metal hydroxide method are normally conducted in the presence of polar aprotic solvents, the phase transfer catalyzed method can be carried out in non-polar solvents due to the employment of a phase transfer catalyst, facilitating incorporation of the salt of an aromatic bishydroxy monomer, (e.g. the diol (D) of formula (I)) in the organic phase.
  • an aromatic bishydroxy monomer e.g. the diol (D) of formula (I)
  • phase transfer catalyzed method is known in the prior art and can be conducted by contacting a substantially equimolar reaction of a double alkali metal salt of a dihydric phenol with a dihalobenzenoid compound, except that the presence of liquid organic sulfone or sulfoxide solvents and cosolvents under substantially anhydrous conditions are not required and phase transfer catalysts are used for this reaction.
  • the poly(arylethersulfone) can be recovered by methods well known and widely employed in the art such as, for example, coagulation, solvent evaporation and the like.
  • the resulting poly(arylethersulfone) polymer may be isolated by devolatilization of the reaction mixture after separation of salts with or without first adding additional solvent(s) such as sulfolane or a mixture of sulfolane with another solvent, optionally the azeotrope solvent, to fully dissolve any polymer and cause the precipitation of the metal halide.
  • the polymer may be isolated by precipitation and/or coagulation by contacting the reaction mixture with a non-solvent for the polymer such as an alcohol or water, or mixtures thereof.
  • the precipitate/coagulate may be rinsed and/or washed with demineralized water prior to drying under reduced pressure and elevated temperature.
  • the resulting precipitate may be further processed by extruding and pelletizing.
  • the pelletized product may subsequently be subjected to further melt processing such as injection moulding and/or sheet extrusion.
  • the conditions for moulding, extruding, and thermoforming the resulting poly(arylethersulfone) are
  • the poly(arylethersulfone) polymer according to the present invention feature all the benefit of the currently sold polysulfones while also unexpectedly featuring a very good resistance to UV light.
  • the diol (D) used to prepare the poly(arylethersulfone) polymer according to the present invention do not show any endocrine activity and are therefore perfect candidates for the preparation of polymers to be used in applications requiring contact with water, food, drugs and/or blood.
  • the present invention also concerns polymer compositions that include at least one of the invented polymers, and at least one other ingredient.
  • Said other ingredient can be another poly(arylethersulfone) polymer. It can also be a polymer other than a poly(arylethersulfone) polymer such as polyvinylpyrrolidone and polyethylene glycol. It can also be a non polymeric ingredient such as a solvent, a filler, a lubricant, a mould release agent, an antistatic agent, a flame retardant, an anti-fogging agent, a matting agent, a pigment, a dye and an optical brightener.
  • a dope solution suitable for the preparation of membranes is intended to denote a solution that is used to prepare a membrane, i.e. by casting, spinning, etc.
  • the poly(arylethersulfone) polymer of the composition according to the present invention has the same characteristics as the poly(arylethersulfone) polymer according to the present invention, in all its embodiments, as above detailed.
  • the polymer composition comprise advantageously more than 1 wt. %, preferably more than 10 wt. %, still more preferably more than 50 wt. %, and the most preferably more than 90 wt. %, related to the total weight of the composition, of the poly(arylethersulfone) polymer.
  • the poly(arylethersulfone) polymer or the polymer composition of the present invention can then be fabricated, e.g. by moulding (injection moulding, extrusion moulding, blow moulding), calendaring or melt spinning into a desired shaped article.
  • the Applicant has surprisingly found that the poly(arylethersulfone) polymer or the polymer composition of the present invention as detailed above, exhibiting excellent properties which are useful in providing high performance polymer membranes.
  • the poly(arylethersulfone) polymer or the polymer composition of the present invention is used for fabrication of membranes.
  • the invention also concerns an article comprising the poly(arylethersulfone) polymer as above described or the polymer composition as above described.
  • the poly(arylethersulfone) polymer and the polymer composition comprised in the article according to the present invention have the same characteristics respectively as the poly(arylethersulfone) polymer and the polymer composition according to the present invention, in all their embodiments, as above detailed.
  • the article may be a membrane.
  • Membranes suitable for the purpose of the invention include, without limitation, isotropic or anisotropic membranes, porous or non-porous membranes, composite membranes, or symmetric or non-symmetric membranes.
  • Such membranes may be in the form of flat structures, corrugated structures, (such as corrugated sheets), tubular structures, or hollow fibers.
  • the membranes according to the present invention can be manufactured using any of the conventionally known membrane preparation methods, for example, by a solution casting or solution spinning method.
  • Non limitative examples of membrane applications include water purification, wastewater treatment, pharmaceutical production, blood purification, in particular hemodialysis and a variety of industrial process separations, such as food and beverage processing, electropaint recovery and gas separation.
  • the above described article may also be a food contact article such as a plumbing article such as a fitting, a valve, a manifold or a faucet, a food tray, a water bottle or a baby bottle, a cookware.
  • a food contact article such as a plumbing article such as a fitting, a valve, a manifold or a faucet, a food tray, a water bottle or a baby bottle, a cookware.
  • the above described article may also be an electronic part.
  • the above described article may also be a housing or cover for a mobile electronic device.
  • the above described article may also be a medical tray or an animal cage.
  • the Applicant has surprisingly found that the poly(arylethersulfone) polymer or the polymer composition of the present invention as detailed above, exhibiting excellent UV properties which is useful in optical applications.
  • the above described article may also be optical articles such as notably sunglass lenses, eyeglass lenses, optical lenses, optical discs.
  • the Applicant has surprisingly found that the poly(arylethersulfone) polymer or the polymer composition of the present invention as detailed above, exhibiting excellent weathering performance which can be used for manufacturing of sheets and films.
  • Another object of the invention is a method for coating substrates comprising using the poly(arylethersulfone) polymer or the polymer composition of the present invention as detailed above.
  • substrates are not particularly limited. Such coatings may be useful for protecting substrates such as notably metals such as steel, in particular stainless steel, aluminum, copper, and other metals in applications such as food and beverage can coatings, marine-hull protection, aerospace, automotive, wire coating, electronics, optical and plastics.
  • substrates such as notably metals such as steel, in particular stainless steel, aluminum, copper, and other metals in applications such as food and beverage can coatings, marine-hull protection, aerospace, automotive, wire coating, electronics, optical and plastics.
  • Udel® polysulfone polymer (P3500) commercially available from SOLVAY SPECIALTY POLYMERS USA, LLC was used for preparing membrane and films for UV exposure and contact angle measurements.
  • RADEL® R PPSU (R5100) commercially available from SOLVAY SPECIALTY POLYMERS USA, LLC.
  • the GPC method was performed using two 5 ⁇ m mixed-D Size Exclusion Chromatography columns from Polymer Laboratories at room temperature. A Waters 2695 separation module with pump and autoinjector was used. A flow rate of 1.5 ml/min was maintained. The polymer solution, 25-50 mg of the polymer in 10 ml methylene chloride was prepared. 15 ⁇ l of the polymer solution was injected. Methylene chloride was used as the mobile phase. An ultraviolet detector at wavelength of 254 nm was used to obtain chromatogram. Waters software (Empower Pro GPC) was used for calibration using polystyrene standards (Easycal PS2 from Agilent), data acquisition, and data analysis. Peak integration start and end points were manually determined from significant difference on global baseline.
  • DSC measurements were done according to ASTM D3418-03, E1356-03, E793-06, E794-06 on TA Instruments Q20 with nitrogen as carrier gas (99.998 % purity, 50 mL/min). Temperature and heat flow calibrations were done using indium. Sample size was 2 to 7 mg.
  • the glass transition temperature was measured on the polymeric material powder from the 2 nd heat thermogram according to the ASTM D3418, by drawing a baseline before the transition and a baseline after the transition : the Tg is the temperature at half height between these two lines.
  • the upper temp was 350°C instead of 300°C.
  • Polymer films were casted from a 20 % NMP solution of the poly(arylethersulfone) polymers of examples 2 and 5, the commercial Udel® polysulfone polymer and Radel® polymer, at room temperature on clean glass plates. A BYK Gardener 6 mil draw bar was used for casting. The glass plates were placed in a vacuum oven at 120°C and dried under vacuum for 24 hours. The films were carefully lifted from glass plates, turned over and further dried for 24 hours at 120°C in a vacuum oven. Before testing, all the films were checked for residual NMP by GC to ensure solvent removal. The residual NMP ranged from 16 - 1284 ppm. Consequently, 100 mm x 10 mm x 30 ⁇ m strips of said film were prepared.
  • polymer films were prepared by casting a 24 % wt/wt DMF polymer solution onto a glass plate that was preheated to 70°C using a 15 mil draw bar (BYK Gardener). The films were then dried at 120°C in a vacuum oven for 48 hours, checked for residual solvent using FT-IR (carbonyl band for DMF at ca. 1680 cm -1 ), and placed into the weatherometer for exposure to ultraviolet light and were then exposed to the conditions as detailed below.
  • FT-IR carbonyl band for DMF at ca. 1680 cm -1
  • the experimental data is showing the relationship between optical clarity (% Transmission) and UV exposure time.
  • the prepared 100 mm x 10 mm x 30 ⁇ m strips of said polymer film was first mounted to metal specimen holders (Atlas SL-3T). The mounted samples were then exposed to the conditions as detailed above for an extended period of time (see Table 1). Throughout this time period, in particular after 24, 29, 48, 72, 84 and 144 hours respectively, samples of exposed film were removed and transmission spectra were measured. Transmission spectra were collected using a Perkin Elmer lambda 950 UV/Vis spectrophotometer set to a slit width of 2 nm while scanning from 200 nm to 600 nm.
  • a 25 mm/min cross-head speed was used.
  • the gage length of films use as control (before UV exposure) was 50 mm, while it was 30 mm for films after 72 hours of UV exposure.
  • the experimental results are summarized in Table 1.
  • Porous membranes were formed by casting a 20 %w/w solution (in what??) of the poly(arylethersulfone) polymers of examples 2 and 5 and the commercial Udel® polysulfone polymer onto a glass plate at 40°C using a 1mil BYK Gardner draw bar. The glass plate was then immediately immersed into a water bath (at 40°C) to form a porous membrane by phase inversion. Comparative water flux data were obtained using an Amicon test cell connected to a water reservoir, which could be pressurized with nitrogen ranging from 10 to 40 psi. The experimental results are summarized in Table 1.
  • poly(arylethersulfone) polymers of examples 4, 5, 8 and the commercial Udel® polysulfone polymer were compression molded into 4 in x 4 in x 0.125 in plaques.
  • the 4 in x 4 in x 0.125 in compression molded plaques of said polymers were machined into Type V ASTM tensile specimens and these specimens of the various polymers were subjected to tensile testing according to ASTM method D638. The testing speed was 0.5"/min.
  • Izod impact testing was conducted on notched samples with a notch radius ranged from 0.398 to 0.402" and pendulum capacity of 2 ftlb according to ASTMD256.

Claims (14)

  1. Poly(arylethersulfon)polymer, das im Wesentlichen aus Wiederholungseinheiten, die aus der direkten Reaktion wenigstens einer aromatischen Dihalogenverbindung, die wenigstens eine -S(=O)2-Gruppe umfasst, und wenigstens einem Diol (D) mit der allgemeinen Formel (I) abgeleitet sind, besteht,

            HO-Q-OH     (I)

    wobei Q eine Gruppe ist, die von 4 bis 30 Kohlenstoffatome umfasst, vorzugsweise von 8 bis 15, die wenigstens eine cycloaliphatische Einheit (M) umfasst, mit der Maßgabe, dass die cycloaliphatische Einheit (M) kein Heteroatom in dem Ring umfasst, und das Poly(arylethersulfon)polymer ein anzahlgemitteltes Molekulargewicht (Mn) von über 8.000 aufweist.
  2. Poly(arylethersulfon)polymer gemäß Anspruch 1, wobei die aromatische Dihalogenverbindung, die wenigstens eine -S(=O)2-Gruppe umfasst, eine Verbindung der allgemeinen Formel (II) ist:

            X-[Ar3-SO2-Ar4]-[Ar5]n-[Ar3-SO2-Ar4]m-X     (II)

    wobei n und m unabhängig 0, 1, 2, 3 oder 4 sind;
    wobei X ein Halogen ausgewählt aus Chlor, Fluor, Brom und Iod ist;
    wobei Ar3, Ar4 gleich oder voneinander verschieden sind und aromatische Einheiten der Formel:
    Figure imgb0029
     sind,
    wobei Ar5 ausgewählt ist aus der Gruppe bestehend aus :
    Figure imgb0030
     wobei jedes Ri unabhängig ausgewählt ist aus der Gruppe bestehend aus :
    Wasserstoff, Halogen, Alkyl, Alkenyl, Alkinyl, Aryl, Ether, Thioether, Carbonsäure, Ester, Amid, Imid, Alkali- oder Erdalkalimetallsulfonat, Alkylsulfonat, Alkali- oder Erdalkalimetallphosphonat, Alkylphosphonat, Amin und quaternärem Ammonium, und i 0, 1, 2, 3 oder 4 ist.
  3. Poly(arylethersulfon)polymer gemäß Anspruch 2, wobei die Verbindung der allgemeinen Formel (II) ausgewählt ist aus 4,4'-Dichlordiphenylsulfon und 4,4'-Difluordiphenylsulfon.
  4. Poly(arylethersulfon)polymer gemäß einem der Ansprüche 1 bis 3, wobei das wenigstens eine Diol (D) ausgewählt ist aus der Gruppe bestehend aus jenen, die den Formeln (D-1), (D-2), (D-3) und (D-4) entsprechen :
    Figure imgb0031
    Figure imgb0032
    Figure imgb0033
     und
    Figure imgb0034
  5. Poly(arylethersulfon)polymer gemäß einem der Ansprüche 1 bis 3, wobei das wenigstens eine Diol (D) von Formel (D-5) ist:
    Figure imgb0035
  6. Poly(arylethersulfon)polymer gemäß einem der Ansprüche 1 bis 5, wobei das anzahlgemittelte Molekulargewicht (Mn) gleich oder kleiner als 120000 ist.
  7. Verfahren zum Herstellen des Poly(arylethersulfon)polymers gemäß einem der Ansprüche 1 bis 6.
  8. Polymerzusammensetzung, umfassend das Poly(arylethersulfon)polymer gemäß einem der Ansprüche 1 bis 6 und wenigstens einen anderen Bestandteil ausgewählt aus einem Polymer, einem Lösungsmittel, einem Füllstoff, einem Gleitmittel, einem Formtrennmittel, einem antistatischen Mittel, einem Flammhemmer, einem Antibeschlagmittel, einem Mattierungsmittel, einem Pigment, einem Farbstoff und einem optischen Aufheller.
  9. Polymerzusammensetzung gemäß Anspruch 8, dadurch gekennzeichnet, dass sie eine Dotierstofflösung ist, die für die Herstellung von Membranen geeignet ist.
  10. Gegenstand, umfassend das Poly(arylethersulfon)polymer gemäß einem der Ansprüche 1 bis 6.
  11. Gegenstand gemäß Anspruch 10, dadurch gekennzeichnet, dass er eine Membran ist, die ausgewählt ist aus der Gruppe bestehend aus isotropen oder anisotropen Membranen, porösen oder nichtporösen Membranen, Verbundmembranen und symmetrischen oder nichtsymmetrischen Membranen.
  12. Gegenstand gemäß Anspruch 11, wobei die Membran in einer Konfiguration ausgewählt aus der Gruppe bestehend aus einer flachen Struktur, einer gewellten Struktur, einer rohrförmigen Struktur und einer Hohlfaser vorliegt.
  13. Gegenstand gemäß Anspruch 11 oder 12, wobei die Membran eine Hämodialysemembran ist.
  14. Gegenstand gemäß Anspruch 10, dadurch gekennzeichnet, dass sie ein Gegenstand für Lebensmittelkontakt ist, wie z. B. ein Speisetablett, eine Wasserflasche oder eine Babyflasche.
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